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At least 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Synthesis of Bismuth Functionalized Grapheme Oxide for Radioactive Iodine Gas Removal - 16114

Released radioactive iodine from nuclear reactors and nuclear severe accidents, such as those experienced at Chernobyl and Fukushima, is one of the most hazardous materials and can affect human health. Uptake of radioactive iodine from gaseous and aqueous waste, consisting of mainly organic forms such as methyl iodide and elemental iodine after reacting with organic matter in scrubber process, is a recent concern during nuclear power plant operation. In general, Triethylenediamine (TEDA) or KI-impregnated activated carbons, silver-loaded silica aerogels, and silver-loaded zeolite are used to remove radioactive iodine compounds. However, previous research has shown TEDA and KI-impregnated activated carbons to have some limitations for use in responding to severe accidents or in pressurized-water reactors, because they are easily burned up and the iodine removal efficiency of silver-loaded sorbents is greatly decreased at high temperatures. To improve the capability of synthesized sorbent material used in iodine gas removal, highly efficient sorbents for methyl and elemental iodine removal were prepared through the functionalization of graphene oxide (GO) with bismuth. GO was synthesized from natural graphite powder (99.95%) by the modified Hummers method, and then mixed with Bi(NO{sub 3}){sub 3}.5H{sub 2}O. After developing a sorbent for the removal of iodine, the synthesized sorbent was characterized using x-ray diffraction, a scanning electron microscope/energy dispersive spectrometer, and thermogravimetric analysis/differential scanning calorimetry, and the surface area of sorbents was determined using the BET-N{sub 2} adsorption method. Methyl iodine batch experiments were conducted for 7 days and elemental iodine gas adsorption experiments were conducted at high temperature (190 deg. C) using a carrier gas (air). The final concentration of iodine in batch and off-gas scrubber solutions (0.1 M NaOH) was analyzed using inductively coupled plasma mass spectrometry. The breakthrough curve and decontamination factor values were also investigated using bismuth-functionalized GO and the results were compared with Ag-zeolite, Sn-apatite, and activated carbon. (authors)

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2013

Single-Pass Flow-Through Test Elucidation of Weathering Behavior and Evaluation of Contaminant Release Models for Hanford Tank Residual Radioactive Waste

Contaminant release models are required to evaluate and predict long-term environmental impacts of even residual amounts of high-level radioactive waste after cleanup and closure of radioactively contaminated sites such as the DOE’s Hanford Site. More realistic and representative models have been developed for release of uranium, technetium, and chromium from Hanford Site tanks C-202, C-203, and C-103 residual wastes using data collected with a single-pass flow-through test (SPFT) method. These revised models indicate that contaminant release concentrations from these residual wastes will be considerably lower than previous estimates based on batch experiments. For uranium, a thermodynamic solubility model provides an effective description of uranium release, which can account for differences in pore fluid chemistry contacting the waste that could occur through time and as a result of different closure scenarios. Under certain circumstances in the SPFT experiments various calcium rich precipitates (calcium phosphates and calcite) form on the surfaces of the waste particles, inhibiting dissolution of the underlying uranium phases in the waste. This behavior was not observed in previous batch experiments. For both technetium and chromium, empirical release models were developed. In the case of technetium, release from all three wastes was modeled using an equilibrium Kd model. For chromium release, a constant concentration model was applied for all three wastes.

chromium↗
DOE OSTI2020

Chapter 3 - Harvesting Thermal Energy with Ferroelectric Materials

Thermal energy is considered the ubiquitous form of energy as all other forms of energy ultimately degrade to thermal energy. Thermal to electrical energy conversion is currently an important method for electricity generation. The traditional power cycles, however, become technically and economically unviable when heat source temperature reduces below 100 °C. Thermal energy harvesting has been proposed as a viable alternative for low-grade thermal to electrical energy conversion. Thermal energy harvesting is a method of generating electricity using temperature-induced variations in material properties. It is particularly useful when the heat sources are available free-of-cost, either in the form of natural heat or waste heat. While there are several thermal energy harvesting techniques, pyroelectricity is the most promising as it can be used in situations where spatial thermal gradients are difficult to establish or the temperature of the heat source is changing. Despite the fact that the pyroelectric effect in ferroelectric materials has been known for past several decades, thermal energy harvesting using ferroelectric materials has not been much explored in the literature. In this chapter, we would explore various aspects of thermal energy harvesting using ferroelectric materials. We have first established the physics behind ferroelectricity, then provided a detailed description on ferroelectric thermal energy harvesting, discussed various ferroelectric thermodynamic cycles and devices proposed in the literature, and finally described various other emerging applications of ferroelectricity.

DIRECT ENERGY CONVERSION,MATERIALS SCIENCE,OTHER I↗
DOE OSTI2019

Pertechnetate (TcO 4 - ) sequestration from groundwater by cost-effective organoclays and granular activated carbon under oxic environmental conditions

Technetium-99 (Tc-99) is a major risk driver at nuclear power plants and several US Department of Energy (DOE) sites. Pertechnetate (TcO4-), the most common chemical form present in liquid nuclear waste and the environment, displays limited adsorption onto sediments, making it highly mobile and difficult to immobilize. In this work, inexpensive organoclays and granular activated carbon (GAC) were investigated for TcO(4)(- )sequestration from artificial groundwater (AGW). The Tc adsorption capacities were 15 mg/g for organoclays and 25 mg/g for GAC from pH 3-12 AGW under oxic conditions. Competitive NO3- at two orders of magnitude greater concentration than TcO4- reduced the Tc adsorption capacity by only 9-25%. In addition, the adsorbed Tc was effectively desorbed by KI, but not Na2SO4, and the regenerated sorbents retained their Tc removal capacity. X-ray absorption spectroscopy demonstrated that the Tc species bound to the organoclays and GAC was Tc(VII) (i.e., TcO4-), rather than Tc(IV). Thus, the inexpensive organoclays and GAC are highly effective at sequestering Tc-99 in its naturally existing TcO4- without requiring costly reductive systems, which may provide a practical solution for removing (TcO4-)-Tc-99 from environmental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A comparative analysis of numerical approaches for the description of gas flow in clay-based repository systems: From a laboratory to a large-scale gas injection test

There is nowadays a consensus among many countries that geological disposal is a favourable solution for the long-term management. Although different host formations and different barrier systems are under consideration around the world, clay-based materials form an important component for waste isolation in most national programmes. Hence, a good comprehension of the effect of gas flow on the hydro-mechanical behaviour of clay-based soils is essential, both at laboratory and field scale. Task B under the international cooperative project DECOVALEX-2023 has recently shown that, after some enhancement, models can be employed to reproduce laboratory scale tests, even with different sample geometries 37 . However, further work is required to understand whether they can be applied to simulate a large-scale experiment. Up-scaling of models for the advective transport of gas through clay-based low permeable material presents a number of problems related to the difficulty in obtaining consistent hydrogeological parameters and constitutive relationships at both laboratory and field scale. Based on a unique dataset from a large-scale gas injection test (Lasgit) performed at the Äspö Hard Rock Laboratory (Sweden), Task B within DECOVALEX-2023 has explored the refinement of these numerical strategies applied to the simulation of gas flow. Work performed within the task reveals that codes do not need to be substantially modified from the laboratory models to reproduce full-scale tests: indeed, model parameters calibrated and validated at laboratory scale have been applied to predict field scale gas flow at Lasgit, including peak gas pressure and injected cumulative gas volume. By means of (1) the introduction of interfaces between blocks to reflect the experimental configuration and the (2) adjustment of some parameters (e.g., higher permeability), the updated models are able to represent most of the key features observed in the experimental data, even at a large scale.

Tamayo-Mas, E↗
DOE OSTI2024

Viscosity of transient glass-forming melt and its relation to foaming during batch-to-glass conversion

Primary foam, which affects the heat transfer into the glass batch and the final glass quality, occurs when a sufficient quantity of transient glass-forming melt evolves with viscosity low enough to close the open porosity of the reacting glass batch. To better understand how the fraction of transient melt and its viscosity affect the primary foam temperature range, we determined, with x-ray diffraction, the fraction and composition of the transient glass-forming melt in a heated waste glass melter feed as a function of temperature. Then we prepared a set of transient melts that occurred within the foaming temperature interval and measured their viscosities with spindle and falling sphere viscometers. Further, the results agree with the Adam-Gibbs and VFT viscosity-composition models, even for transient melt compositions outside of the models compositional validity range. As silica and other refractory particles dissolved in the predominantly borate transient melt while temperature increased, viscosity increased from the initial value of ~500 Pa s at the onset of foaming (~650°C) to a maximum of ~770 Pa s when silica dissolution was almost complete (~700°C). As temperature increased further, transient melt viscosity decreased to ~220 Pa s (~850°C) when the primary foam collapsed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Upcycling and urban mining for nanomaterial synthesis

Responsible processing of complex waste streams, especially through resource recovery and upgrading, is essential to lessen the environmental and societal impacts of materials production and disposal. Upcycling waste into materials that have higher value than their original form, and urban mining, the recovery of metals from electronic waste, are two recent strategies in waste management. Sustainable cradle-to-grave manufacturing means recovering resources that would otherwise contaminate the planet. Here, we discuss upcycling of plastic, rubber, and related carbon waste streams into graphene, as well as the recovery of precious metals and rare earth elements, while removing toxic heavy metals, all using flash Joule heating. Furthermore, this article provides a brief overview of the current state of upcycling and urban mining as it applies to materials conversion, recovery, or nanomaterial synthesis, with a concluding perspective highlighting the considerations, opportunities, and challenges that accompany upcycling and urban mining research.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

A shift between mineral and nonmineral sources of iron and sulfur causes proteome-wide changes in Methanosarcina barkeri

ABSTRACT Iron (Fe) and sulfur (S) are required elements for life, and changes in their availability can limit the ecological distribution and function of microorganisms. In anoxic environments, soluble Fe typically exists as ferrous iron [Fe(II)] and S as sulfide (HS − ). These species exhibit a strong affinity that ultimately drives the formation of sedimentary pyrite (FeS 2 ). Recently, paradigm-shifting studies indicate that Fe and S in FeS 2 can be made bioavailable by methanogens through a reductive dissolution process. However, the impact of the utilization of FeS 2 , as opposed to canonical Fe and S sources, on the phenotype of cells is not fully understood. Here, shotgun proteomics was utilized to measure changes in the phenotype of Methanosarcina barkeri MS grown with FeS 2 , Fe(II)/HS − , or Fe(II)/cysteine. Shotgun proteomics tracked 1,019 proteins overall, with 307 observed to change between growth conditions. Functional characterization and pathway analyses revealed these changes to be systemic and largely tangential to Fe/S metabolism. As a final step, the proteomics data were viewed with respect to previously collected transcriptomics data to deepen the analysis. Presented here is evidence that M. barkeri adopts distinct phenotypes to exploit specific sources of Fe and S in its environment. This is supported by observed protein abundance changes across broad categories of cellular biology. DNA adjacent metabolism, central carbon metabolism methanogenesis, metal trafficking, quorum sensing, and porphyrin biosynthesis pathways are all features in the phenotypic differentiation. Differences in trace metal availability attributed to complexation with HS − , either as a component of the growth medium [Fe(II)/HS − ] or generated through reduction of FeS 2 , were likely a major factor underpinning these phenotypic differences. IMPORTANCE The methanogenic archaeon Methanosarcina barkeri holds great potential for industrial bio-mining and energy generation technologies. Much of the biochemistry of this microbe is poorly understood, and its characterization will provide a glimpse into biological processes that evolved close to life’s origin. The discovery of its ability to extract iron and sulfur from bulk, solid-phase minerals shifted a longstanding paradigm that these elements were inaccessible to biological systems. The full elucidation of this process has the potential to help scientists and engineers extract valuable metals from low-grade ore and mine waste generating energy in the form of methane while doing so.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)

This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1992

The Tharsis Montes, Mars - Comparison of volcanic and modified landforms

The three Tharsis Montes shield volcanos, Arsia Mons, Pavonis Mons, and Ascraeus Mons, have broad similarities that have been recognized since the Mariner 9 reconnaissance in 1972. Upon closer examination the volcanos are seen to have significant differences that are due to individual volcanic histories. All three volcanos exhibit the following characteristics: gentle (less than 5 deg) flank slopes, entrants in the northwestern and southeastern flanks that were the source for lavas extending away from each shield, summit caldera(s), and enigmatic lobe-shaped features extending over the plains to the west of each volcano. The three volcanos display different degrees of circumferential graben and trough development in the summit regions, complexity of preserved caldera collapse events, secondary summit-region volcanic construction, and erosion on the lower western flanks due to mass wasting and the processes that formed the large lobe-shaped features. All three lobe-shaped features start at elevations of 10 to 11 km and terminate at 6 km. The complex morphology of the lobe deposits appear to involve some form of catastrophic mass movement followed by effusive and perhaps pyroclastic volcanism.

Zimbelman, James R.↗
NASA NTRS2014

The Fleet Application for Scheduling and Tracking (FAST) Management Website

The FAST application was designed to replace the paper and pen method of checking out and checking in GSA Vehicles at KSC. By innovating from a paper and pen based checkout system to a fully digital one, not only the resources wasted by printing the checkout forms have been reduced, but it also reduces significantly the time that users and fleet managers need to interact with the system as well as improving the record accuracy for each vehicle. The vehicle information is pulled from a centralized database server in the SPSDL. In an attempt to add a new feature to the FAST application, the author of this report (alongside the FAST developers) has been designing and developing the FAST Management Website. The GSA fleet managers had to rely on the FAST developers in order to add new vehicles, edit vehicles and previous transactions, or for generating vehicles reports. By providing an easy-to-use FAST Management Website portal, the GSA fleet managers are now able to easily move vehicles, edit records, and print reports.

Object-Oriented Programming↗
NASA NTRS1991

Plants for water recycling, oxygen regeneration and food production

During long-duration space missions that require recycling and regeneration of life support materials the major human wastes to be converted to usable forms are CO2, hygiene water, urine and feces. A Controlled Ecological Life Support System (CELSS) relies on the air revitalization, water purification and food production capabilities of higher plants to rejuvenate human wastes and replenish the life support materials. The key processes in such a system are photosynthesis, whereby green plants utilize light energy to produce food and oxygen while removing CO2 from the atmosphere, and transpiration, the evaporation of water from the plant. CELSS research has emphasized the food production capacity and efforts to minimize the area/volume of higher plants required to satisfy all human life support needs. Plants are a dynamic system capable of being manipulated to favour the supply of individual products as desired. The size and energy required for a CELSS that provides virtually all human needs are determined by the food production capacity. Growing conditions maximizing food production do not maximize transpiration of water; conditions favoring transpiration and scaling to recycle only water significantly reduces the area, volume, and energy inputs per person. Likewise, system size can be adjusted to satisfy the air regeneration needs. Requirements of a waste management system supplying inputs to maintain maximum plant productivity are clear. The ability of plants to play an active role in waste processing and the consequence in terms of degraded plant performance are not well characterized. Plant-based life support systems represent the only potential for self sufficiency and food production in an extra-terrestrial habitat.

NASA Discipline Life Support Systems↗
DOE OSTI2012

Evaluation of Waste Heat Recovery and Utilization from Residential Appliances and Fixtures

Executive Summary In every home irrespective of its size, location, age, or efficiency, heat in the form of drainwater or dryer exhaust is wasted. Although from a waste stream, this energy has the potential for being captured, possibly stored, and then reused for preheating hot water or air thereby saving operating costs to the homeowner. In applications such as a shower and possibly a dryer, waste heat is produced at the same time as energy is used, so that a heat exchanger to capture the waste energy and return it to the supply is all that is needed. In other applications such as capturing the energy in drainwater from a tub, dishwasher, or washing machine, the availability of waste heat might not coincide with an immediate use for energy, and consequently a heat exchanger system with heat storage capacity (i.e. a regenerator) would be necessary. This study describes a two-house experimental evaluation of a system designed to capture waste heat from the shower, dishwasher clothes washer and dryer, and to use this waste heat to offset some of the hot water energy needs of the house. Although each house was unoccupied, they were fitted with equipment that would completely simulate the heat loads and behavior of human occupants including operating the appliances and fixtures on a demand schedule identical to Building American protocol (Hendron, 2009). The heat recovery system combined (1) a gravity-film heat exchanger (GFX) installed in a vertical section of drainline, (2) a heat exchanger for capturing dryer exhaust heat, (3) a preheat tank for storing the captured heat, and (4) a small recirculation pump and controls, so that the system could be operated anytime that waste heat from the shower, dishwasher, clothes washer and dryer, and in any combination was produced. The study found capturing energy from the dishwasher and clothes washer to be a challenge since those two appliances dump waste water over a short time interval. Controls based on the status of the dump valve on these two appliances would have eliminated uncertainty in knowing when waste water was flowing and the recovery system operated. The study also suggested that capture of dryer exhaust heat to heat incoming air to the dryer should be examined as an alternative to using drying exhaust energy for water heating. The study found that over a 6-week test period, the system in each house was able to recover on average approximately 3000 W-h of waste heat daily from these appliance and showers with slightly less on simulated weekdays and slightly more on simulated weekends which were heavy wash/dry days. Most of these energy savings were due to the shower/GFX operation, and the least savings were for the dishwasher/GFX operation. Overall, the value of the 3000 W-h of displaced energy would have been $0.27/day based on an electricity price of $.09/kWh. Although small for today s convention house, these savings are significant for a home designed to approach maximum affordable efficiency where daily operating costs for the whole house are less than a dollar per day. In 2010 the actual measured cost of energy in one of the simulated occupancy houses which waste heat recovery testing was undertaken was $0.77/day.

Tomlinson, John J.↗
DOE OSTI2017

Ruthenium Volatilisation in Nuclear Waste Systems -Comparison of Ru(III)Cl{sub 3} and Ru(III)NO(NO{sub 3}){sub 3} - 17113

Ruthenium is a fission product possessed of two relatively long lived isotopes; {sup 103}Ru and {sup 106}Ru, both of which form part of the Highly Active (HA) waste raffinate during spent nuclear fuel reprocessing. During reprocessing, ruthenium, which may be in the form of the RuNO{sub 3}+ complex, encounters temperatures conducive to volatilisation. Due to ruthenium's high specific radioactivity it is important to understand the mechanism by which volatilisation occurs. Here we use combined cyclic voltammetry (CV) and electrochemical micro-gravimetry experiments in a study of both NO free Ru (III), in the form of a RuCl{sub 3} solution and NO complexed Ru (III), in the form of RuNO{sub 3}+ solutions. We do this in order to establish baseline behaviour of NO free Ru (III) and compare it to NO complexed Ru (III) to determine the effect of complexation on the system. We have observed discrete oxidations in both systems from solution phase Ru (III) to solid phase RuO{sub 2} and volatile RuO{sub 4}. Two key differences emerged between the two systems, the first being the mass changes associated with deposition and stripping of RuO{sub 2} are significantly smaller in the RuNO{sub 3}+ solutions than those for solutions of RuCl{sub 3}. The second difference is the difference in onset of volatile RuO{sub 4} generation, in the RuNO{sub 3}+ solution, RuO{sub 4} generation is 100 mV positive than that for the RuCl{sub 3} solution. This suggests NO complexation protects Ru (III) against oxidation and, to a certain extent, volatilisation as RuO{sub 4}. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Nanocrystallography measurements of early stage synthetic malaria pigment

The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data. If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.

36 MATERIALS SCIENCE↗
DOE OSTI2019

The Development of a Small-Scale Project Model for Waste Management at the Port Hope Conversion Facility - 19126

Cameco Corporation's (Cameco) Port Hope Conversion Facility (PHCF) was previously owned by the federal Crown Corporation, Eldorado Nuclear, which held a significant inventory of legacy waste material at the time Cameco was formed in 1988. Over time, Cameco's ongoing operations contributed to an increase in the volume of low-level radioactive waste managed onsite. Since 2011, Cameco has completed annual waste management campaigns with the goal of accelerating the recycle/disposal of accumulated legacy radioactive wastes stored at its Ontario operations. With disposal options for low-level radioactively contaminated wastes in Canada limited due to cost considerations and no commercially accessible landfills licensed for radioactive material. In recent years, Cameco has started to ship marginally contaminated wastes (<500 ppm uranium) to the United States for disposal in an appropriate landfill owned by US Ecology in Idaho. Numerous successful campaigns totaling over 1,000 successful shipments, have been completed to transport drummed and/or bagged material by rail in gondola cars to the disposal facility in Idaho since 2011. All shipments have been completed in compliance with all environmental regulations, with a perfect compliance record maintained to date. To achieve this excellent compliance record, the campaigns require careful planning by both organizations, as well as deployment of personnel from the Idaho facility during the campaign for project management, characterization and/or radiation monitoring support. As the accumulated waste inventory has been reduced through these projects, the scope and duration of each campaign has also decreased. In the last few years, road transport directly to the Idaho facility has also been utilized. This option allows for the deployment of small projects that may be completed for a smaller inventory of a specific waste type and to manage newly-generated low-level radioactive wastes on an ongoing basis. These projects have ranged from a single standard van shipment to multiple trucks running continuous loops between the Ontario and Idaho or Ontario and an intermediary site and have been utilized for marginally contaminated wastes (<500 ppm uranium) as well as marginally contaminated wastes with additional hazard classification. Cameco and US Ecology personnel have collaborated to develop characterization and shipment procedures that enable these projects to be executed in full compliance with all Canadian and US regulations, without deployment of personnel from the Idaho facility, while maintaining adequate oversight by both organizations to ensure that the waste is safely and compliantly managed. These protocols have been implemented and optimized for the Port Hope Conversion Facility and will be rolled out to other Cameco facilities in Ontario through 2019. Cameco expects to utilize the small project model for the long term to ensure that eligible marginally contaminated wastes (<500 ppm uranium) are managed appropriately to ensure that once the legacy material is eliminated, it remains so. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Total Mercury Analysis of Radioactive Waste Containing Multiple Mercury Species

In this work, a direct mercury analyzer (DMA) was used to analyze total mercury in radioactive waste samples containing methylmercury and other forms of mercury including Hg o (elemental) together with inorganic ionic mercury species and complexes. These samples were also analyzed using Cold Vapor Atomic Absorption Spectroscopy (CVAAS) and/or Inductively Coupled Plasma Mass Spectroscopy (ICMS). Comparative statistical evaluation of the results from spike solutions/simulants, liquid radioactive waste samples, and interlaboratory performance test samples demonstrated that the various methods generated accurate and/or equivalent total mercury data and equivalent precision (2σ ± < 20%). Triplicate total mercury analysis of an exemplar radioactive waste resulted in an average value of 54.1 mg/L (as Hg) using CVAAS, 55.1 mg/L using ICPMS and 56.0 mg/L using DMA. A primary advantage of the DMA in a radioactive environment is avoiding multi-step, labor-intensive, time-consuming and waste-producing sample preparation protocols needed for CVAAS and ICPMS. DMA was determined to be the preferred method for measuring total mercury in the Savannah River National Laboratory (SRNL) radioanalytical laboratory based on analytical performance combined with ease of use in a radiological containment unit.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

Among radioactive constituents present in the tank waste stored at the U.S. DOE Hanford Site, technetium-99 (Tc), which is generated from the fission of 235 U and 239 Pu in high yields, presents a unique challenge in that it has a long half-life ( = 292 keV; T1/2 = 2.11105 y) and exists predominately in soluble forms in the liquid supernatant and salt cake fractions of the waste. In the strongly alkaline environments prevalent in most of the tank waste, its dominant chemical form is pertechnetate (TcO 4 - , oxidation state +7). However, attempts to remove Tc from the Hanford tank waste using ion-exchange processes specific to TcO 4 - only met with limited success, particularly when processing tank waste samples containing elevated concentrations of organic complexants. This suggests that a significant fraction of the soluble Tc can be present as low-valent Tc (oxidation state < +7) (non-pertechnetate). The chemical identities of these non-pertechnetate species are poorly understood. Previous analysis of the SY-101 and SY-103 tank waste samples provided strong evidence that non-pertechnetate can be comprised of [fac-Tc(CO) 3 ] + complexes containing Tc in oxidation state +1 (Lukens et al. 2004). During the last three years, our team has expanded this work and demonstrated that high-ionic-strength solutions typifying tank waste supernatants promote oxidative stability of the [fac-Tc(CO) 3 ] + species (Rapko et al. 2013a; 2013b; Levitskaia et al. 2014; Chatterjee et al. 2015). Obtained results also suggest possible stabilization of Tc(VI) and potentially Tc(IV) oxidation states in the high-ionic-strength alkaline matrices particularly in the presence of organic chelators, so that Tc(IV, VI) can serve as important redox intermediates facilitating the reduction of Tc(VII) to Tc(I). Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. The key FY 2016 results are summarized below.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗